Prof. Dr.
Muhammad Zamir Hossain
(ড. মুহাম্মদ জামির হোসেন)
PhD in Chem. Eng., Tohoku Univ., Japan
Adjunct Faculty Member
Dept. of Chemistry, BUET
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CHEM 111 : Inorganic Chemistry
MZH:
Modern theories of acids and bases;
Different types of chemical bonds,
molecular geometry,
Modern concept of bonding: valance bond theory and
molecular orbital theory.
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Reference Books
• Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
• General Chemistry by D.D. Ebbing
• Introduction to Modern Inorganic Chemistry by S.Z Haider
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Modern theories of
Acids and Bases
or general chemistry, analytical
and a whole lot more!
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HISTORY
• By the early 19th century, many acids that do not contain
oxygen were known. By 1838, Liebig defined acids as
"compounds containing hydrogen, in which the hydrogen
can be replaced by a metal,"
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Arrhenius acid is a substance that produces H+ (H3O+) in water
Arrhenius base is a substance that produces OH- in water
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A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor
base acid acid base
conjugate conjugate
base acid
acid base
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Acid-Base Properties of Water
H2O (l) H+ (aq) + OH- (aq)
autoionization of water
+ + H -
H O + H O [ H O H ] O
H H H
conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
base
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Molecular Structure and Acid Strength
H X H+ + X-
The The (B-L Theory)
stronger weaker
the bond the acid
HF << HCl < HBr < HI
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Molecular Structure and Acid Strength
d- d+
Z O H Z O - + H+
(B-L Theory)
The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state
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Molecular Structure and Acid Strength
1. Oxoacids having different central atoms (Z) that are from
the same group and that have the same oxidation number.
Acid strength increases with increasing electronegativity of Z
•• ••
O O
••
••
••
••
•• •• •• ••
H O Cl O H O Br O
••
••
•• •• •• •• •• ••
Cl is more electronegative than Br
HClO3 > HBrO3
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Molecular Structure and Acid Strength
2. Oxoacids having the same central atom (Z) but different
numbers of attached groups.
Acid strength increases as the oxidation number of Z increases.
HClO4 > HClO3 > HClO2 > HClO
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Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water
A Brønsted acid is a proton donor
A Lewis acid is a substance that can accept a pair of electrons
A Lewis base is a substance that can donate a pair of electrons
•• ••
H+ + OH- H O H
••
•• ••
acid base
H H
H+ + N H H N H
••
H H
acid base 16
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Lewis Acids and Bases
F H F H Adduct: a
product of the
F B + N H F B N H
••
reaction of a
Lewis acid
F H F H and a base to
form a new
acid base combination
(electrophile) (nucleophile)
No protons donated or accepted!
Let’s look at this reaction, and others like it more closely.
To see what’s really going on we need to look at the MOs.
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Different types of chemical bonds
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Q. Why?
Q. Why?
Q. Why?
Q. Why?
Q. Why?
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Covalent Character of Ionic Compounds
Fazan’s Rule
Related terminology
Polarising power
It is the extent to which a cation can polarise an anion. It is proportional to
charge density. Charge density is the ratio of charge to volume.
Polarising power α Charge density.
The more the charge density, the greater the polarising power for that cation.
Polarisability
It is the extent to which an ion can be polarised. It can also be defined as the
ease with which an ion can be polarised. Polarisation is the distortion of a
spherically symmetric electron cloud to an unsymmetric cloud.
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Postulates of Fazan’s Rule
The rule can be stated on the basis of 3 factors, and they are:
Size of the ion: Smaller the size of the cation, the larger the size of the anion
and the greater the covalent character of the ionic bond.
The charge of cation: Greater the charge of the cation, the greater the
covalent character of the ionic bond.
Electronic configuration: For cations with the same charge and size, the one
with (n-1)dn nso which is found in transition elements, has greater covalent
character than the cation with ns2 np6 electronic configuration, which is
commonly found in alkali or alkaline earth metals.
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Explanation of Fazans’ Rule
Rule 1:
The first rule speaks about the polarising power of the cation. If the cation
is smaller, then we can say that the volume of the ion is less. If the volume
is less, we can conclude that the charge density of the ion would be high.
Since the charge density is high, the polarising power of the ion would be
high. This makes the compound to be more covalent.
Rule 2:
The second rule speaks about the polarizability of the anion. The larger
the anion, the less the effective nuclear charge that holds the valence electron
of the ion in place. Since the last electron is loosely bound in large anions,
it can easily be polarised by a cation, thereby making the compound more
covalent.
Rule 3:
The third rule is a special case. Let us use an example to explain this point.
Example: If we want to find the more covalent compound among HgCl2 and
Calcium Chloride, we cannot use size as a factor to conclude. This is because
both Hg2+ and Ca2+ are of almost equal size. To explain this, we employ the
third rule. The electronic configuration of Hg2+ is 6s0 5d10. This configuration
is called pseudo-octet because the d-orbital is fully filled, but the element
does not have 8 electrons or an octet 33
Explanation of Fazans’ Rule
We know that d orbitals are not good at shielding, so we can say that the anion (Cl –)
would be more polarised because the d orbital is poor at shielding, making HgCl2
more covalent than CaCl2 because Ca2+ ion has a noble gas configuration.
Now, to answer the question that we asked first, among the alkali chlorides,
which one is the most covalent:
Since the anion is the same, we have to compare the cations.
According to Fajans’ rules, the smaller the cation, the more the covalency.
Therefore, LiCl is the most covalent.
Let Us Understand Fajans’ Rule Using a Detailed Illustration
Consider Aluminium Iodide (AlI3)
This is an ionic bond which was formed by the transfer of electrons.
The iodine being bigger, has a lesser effective nuclear charge. Thus, the bonding
electrons are attracted lesser towards the Iodine nucleus.
On the contrary, the aluminium having three positive charges attracts the shared pair
of electrons towards itself.
This leads to insufficient charge separation for it to be ionic, and so it results in the
development of a covalent character in AlI3.
Consider Aluminium Fluoride (AlF3)
This is an ionic bond which was also formed by the transfer of electrons.
But here, the fluorine being smaller attracts the shared pair of an electron more 34
towards itself, and so there is sufficient charge separation to make it ionic.
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Properties of Ionic compounds
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Differences
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Lewis Dot Structure
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Types of Covalent Bonds
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Types of Covalent Bonds
HCl HH
Polar covalent bond exists when the Non-polar covalent bond is formed
electronegativity of combining atoms when two atoms share an equal
differs, resulting in unequal electron number of electrons. The difference
sharing. Electrons will be drawn to in electronegativity between two
more electronegative atoms. The atoms is zero. It occurs whenever
atoms’ electronegative difference is the atoms combined have a similar
greater than zero but less than 2. electron affinity. Found in gas
molecules such as H2, N2 etc. 44
Examples o Polar and Non-polar Covalent Bonds
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3 types of covalent bonds in hydrocarbons
σ σ σ
,
Single Double
Triple
Saturated Unsaturated
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Sigma (σ) and pi (π) bonds
Sigma (σ) and pi (π) bonds are two types of covalent bonds formed through
the overlap of atomic orbitals. Sigma bonds result from head-on overlap, while
pi bonds arise from sideways overlap. A single bond is always a sigma bond,
while double bonds contain one sigma and one pi bond, and triple bonds have
one sigma and two pi bonds.
Sigma (σ) and pi (π) bonds
Which bond is strong/weak and why?
In sigma bonds, the large overlap of the orbital involves the removal of a large
amount of energy. While in pi bonds the extent of overlapping is less than
sigma bond. Therefore, sigma bond is stronger than pi bond. Note: Bond
strength depends on the bond length.
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In chemistry, hybridization is defined as the process of combining two atomic
orbitals to create a new type of hybridised orbitals. The formation of hybrid
orbitals with completely different energies, shapes, and so on is frequently the
outcome of this intermixing.
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Metallic Bond
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Metallic Bond
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Molecular Geometry
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Shapes of molecule with Lone pair of electrons
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Diatomic Molecular Orbital
•
Theory
In the case of diatomic molecules, the interactions are easy to see and
may be thought of as arising from the constructive interference of the
electron waves (orbitals) on two different atoms, producing a bonding
molecular orbital, and the destructive interference of the electron waves,
producing an antibonding molecular orbital
• This Approach is called LCAO-MO
(Linear Combination of Atomic Orbitals to Produce
Molecular Orbitals)
A Little Math is need to understand
Only a Little I promise!
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How to impress your friends and family!
Making Molecular Orbitals
Antibonding
Bonding
In this case, the energies of the A.O.’s are identical 97
Molecular Orbital of H2
The lowest energy state of two isolated hydrogen atoms is two 1s orbitals
each with one electron. As the nuclei approach each other, the lowest
energy state becomes a molecular orbital containing two paired electrons.
This lobe represents the orbital or wavefunction of the electrons delocalized
around the two protons. This is a bond.
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Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).
A bonding molecular orbital has lower energy and greater stability than
the atomic orbitals from which it was formed.
An antibonding molecular orbital has higher energy and lower stability
than the atomic orbitals from which it was formed.
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10.6
An analogy between light waves and atomic
wave functions
Amplitudes of wave
functions are added
Amplitudes of wave
functions are subtracted
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Quantum States in H2 (as computed)
H2 also has other electronic quantum states with corresponding allowed
energies. These molecular orbitals have lobe structures and nodes just
like atomic orbitals.
0.735 Å
R=¥ (H2)
R=¥
This diagram shows (H) (H)
some allowed energy
levels for atomic H 2s 2s
and molecular H2.
(R = ¥ denotes the two
atoms at “infinite
separation” - no bond.)
The orbitals are filled
with electrons starting
with the lowest energy, 1s 1s
just like atoms.
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Quantum States in H2 (as computed)
H2 also has other electronic quantum states with corresponding allowed
energies. These molecular orbitals have lobe structures and nodes just
like atomic orbitals.
R=¥ 0.735 Å
(H) (H2)
2s
1s
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Quantum States in H2: Allowed Energies
First let’s ignore the wavefunctions (orbitals), and consider only the
allowed energies, just as we did with atoms. What do we observe?
R=¥ 0.735 Å
(H) (H2)
2s
1s
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Quantum States in H2
The energy of the H2 molecule is lower than the energy of two isolated H
atoms. That is, the energy change of forming the bond is negative.
R=¥ 0.735 Å We call this molecular orbital a bonding
(H) (H2)
orbital for this very reason.
The other orbitals have higher energies than
2s the atomic orbitals of H.
Electrons in these orbitals would not
contribute to the stability of the molecule.
H2 contains the simplest kind of bond, a pair
of electrons delocalized between two nuclei,
1s symmetric to rotation about the interatomic axis.
s This is known as a sigma (s) bond. 105
Molecular Orbitals in H2
The next-lowest energy orbital is unoccupied. As it lies above the
highest atomic orbital, we refer to it as an anti-bonding orbital.
R=¥ 0.735 Å Look also at the shape of the lobes:
(H) (H2) The anti-bonding orbital has a node between
the two nuclei.
2s Where the bonding orbital has an electron
density build-up between the nuclei, the anti-
bonding orbital would have a reduced
electron density (y 2).
This orbital is called the
Lowest Unoccupied Molecular
s* Orbital (LUMO)
1s
This orbital is called the
Highest Occupied Molecular
s Orbital (HOMO) 106
Molecular Orbital Theory
The solution to the Wave Equation for molecules leads to quantum
states with discrete energy levels and well-defined shapes of electron
waves (molecular orbitals), just like atoms.
Each orbital contains a maximum of two (spin-paired) electrons, just like atoms.
Bonds form because the energy of the electrons is lower in the molecules than it
is in isolated atoms. Stability is conferred by electron delocalization in the
molecule as they are bound by more than one nucleus (longer de Broglie
wavelength).
This gives us a convenient picture of a bond as a pair of shared (delocalized)
electrons. It also suggests some simple (and commonly-used) ways of
representing simple s bonds as:
1. A shared pair of electrons (dots)
H:H
2. A line between nuclei. 107
H-H
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Reaction Mechanisms
How do the atoms of the reactant molecules
rearrange to form the product molecules?
What is the sequence of bond breaking and
bond making?
What are the energetics of the process?
How do the electrons flow?
What molecular orbitals are involved?
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How do you analyze a mechanism?
Follow the Electrons. Push your arrows.
H F
+ H F N
N
H H H H
H H
What orbitals are involved?
What are the important MOs
of HF and NH3?
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Restating the Lewis Acid-Base Definition:
a) Base: has e- pair in HOMO of
correct energy and symmetry
b) Acid: has LUMO of correct energy
and symmetry
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Classes of Lewis bases
(Ligands)
• Monodentate Ligands - A ligand that donates only one
electron pair to a single metal
– One of the best examples is NH3.
• Bridging Ligands - A ligand that donates one or more
electron pairs to two or more metals
– Halides and hydroxide are good examples, since each
possesses two or more electron pairs on the donor atom
– As we considered before, one of the steps to forming insoluble
hydroxide and oxo compounds is the bridging of two metals in
the course of hydroysis.
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Classes of Lewis bases – con’t
• Ambidentate Ligands - Ligands that
possess two or more donor atoms can act
as a monodentate ligand through either
donor atom, or bridge two metals.
• The pseudohalides such as cyanide, azide
and thiocyanate are good examples.
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Denticity
• The number of potential donor interactions
is called the denticity
• ligands are classified as bidentate
chelating ligands (as for ethylenediamine),
hexadentate chelating ligands (as for
ethylenediaminetetraacetic acid; EDTA)
and so forth.
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Chelating ligands
• ethylenediamine (on the left)
yields a five-membered ring
• acetylacetonate (on the right)
yields a six-membered ring
N O
Ni Ni
N O
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Structures of Common Chelating Ligands
N N N N
2,2’-bipyridine (bpy) N 1,10-phenathroline (phen)
N N
terpyridine (terpy)
H2N H2N NH2
H2N NH2 N
NH2 H
ethylenediamine (en) propylenediamine (prn) diethylenetriamine (dien)
H
H2N N
N NH2 N
H
NH2 NH2
H2N
triethylenetetramine (trien)
tri(ethylenediamine)amine (tren)
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Macrocyclic ligands
• Macrocyclic Ligands - A special class of
generally tetradentate chelating ligands, where
the four donor atoms are arranged in a circular
ring array, as in the porphyrins and anes.
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Increasing Topological Constraint
Coordination Chelation Macrocycle Effect Cryptate Effect
NH2
H2N
H H N N N
N N
H
N N N
N
H2N NH2 N N
H H
NH3
H
N NH2
H2N N
H
[Ni(H2O)6]2+ + n L ¾ [Ni(L)n(H2O)2]2+ + 4 H2O
L= NH3 en trien 2,3,2-
n= 4 2 1 1
log bn = 8.12 13.5 13.8 14.6 147
